Keratin fiber dye compounds

ABSTRACT

D R A W I N G WHEREIN N IS 2-6 AND R2 and R3 are lower alkyl having 1-6 carbon atoms, and the quaternary ammonium salt thereof, is useful as hair dyes.   WHEREIN R is selected from the group consisting of lower alkyl, hydroxyalkyl and alkylaminodialkyl, wherein each alkyl moiety has 1-6 carbon atoms and R1 is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl and   A compound of the formula

United States Patent 1 Gregoire et al.

[ KERATIN FIBER DYE COMPOUNDS [75] Inventors: Kalopissis Gregoire, Paris; Bugaut Andree, Boulonge-sur-Seine; Zorayan Vahan, Enghien-les-Bains, all of France [73] Assignee: LOreal, Paris, France [22] Filed: Oct. 7, 1970 [21] Appl. No.: 78,923

Related U.S. Application Data [62] Division of Ser. No. 728,750, May 13, 1968, Pat. No.

[52] U.S. Cl 260/562 A, 260/247.l, 260/293.73, 260/247.2 A, 260/471 A, 260/519,

' 1 260/397.7, 8/10, 8/10.l [51] Int. Cl. C07c 103/12 [58] Field of Search 260/562 A Primary Examiner-Alex Ma zel Assistant ExaminerJose Tovar Attorney-Cushman, Darby & Cushman [111 3,742,048 June 26, 1973 wherein R is selected from the group consisting of lower alkyl, hydroxyalkyl and alkylaminodialkyl, wherein each alkyl moiety has 1-6 carbon atoms and R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl and -(om)nN wherein n is 2-6 and R and R are lower alkyl having 1-6 carbon atoms, and the quaternary ammonium salt thereof, is useful as'hair dyes.

r. 3 Claims, No Drawings KERATIN FIBER DYE COMPOUNDS This is a divisional application of our copending-U.S. Pat. application Ser. No. 728,750, filed May 13, 1968, now US. Pat. No. 3,617,164.

It is an object of the present invention to provide a compound of the formula wherein R is selected from the group consisting of lower alkyl, hydroxyalkyl and alkylaminodialkyl, wherein each alkyl moiety has 1-6 carbon atoms and R is selected from the group consisting of lower alkyl, lower hydroxyalkyl, lower alkoxyalkyl and -(CHz)n-N wherein n is 2-6 and R and R are lower alkyl having 1-6 carbon atoms.

Another object of the present invention is to provide new quaternary derivatives corresponding to the compounds of formula (1), when these compounds have a quaternizable tertiary amine function.

It should be noted that the compounds of formula (1) are particularly adapted to be used to dye keratinic fibers in general, and especially hair. They have an excellent affinity for keratinic fibers, good stability when exposed to light and inclement weather, and are readily soluble in water.

The compounds of formula (1) may be quaternized in a conventional manner, using a quaternizing agent such as methyl sulfate or an alkyl or aryl halide.

In order that the invention may be better understood, several examples of the compounds of formula (1) will now be described.

EXAMPLE 1 Preparation of N-methyl-parachlorometanitraniline by alkylation with arylsulfonamides. First step: alkylation.

0.4 mol (125 g) of 2-nitro-4-benzenesulfonylamino chlorobenzene is dissolved in 600 cc of a normal sodium hydroxide solution at 30 C. 1.6 mols (125 cc) of methyl sulfate are added little by little, while keeping the temperature between 35 and 40 C and the pH value near 9 by successive additions of a normal sodium hydroxide solution. The reaction mixture is then left to stand for 6 hours at room temperature. Cooling, drying and washing then yields 138 g of crude 2-nitro-4-N-methyl-n-benzene sulfonylamino chlorobenzene which, after recrystallization in ethyl acetate, melts at 1 19 C. Analysis of this product shows the following results:

Analysis Calculated for Found C H,,N,ClSO,

Second step: Hydrolysis Found Analysis Calculated for C,H,N,O,C1 C 71 45.08 44.87 44.96 H 71 3.72 3.84 3.87 N% 15.01 15.15-15.25

EXAMPLE 2 Preparation of (N-methyl-N-acetyl)parachlorometanitraniline.

0.19 mol of N-methyl-parachlorometanitraniline, prepared as set forth in example 1, is dissolved in 70 cc of acetic anhydride. This is heated for 15 minutes in a boiling water-bath, and poured into 700 cc of water. Drying then yields 35 g of 2-nitro-4-(N-methyl-N- acetyl)amine chlorobenzene, which melts at 1 14 C.

EXAMPLE 3 5 Preparation of l-'y-methoxypropylamino-2-nitro-4-(N- methyl-N-acetyl)-amino benzene.

0.1 mol (22.9 g) of (N-methyl-N-acetyl)parachlorometanitraniline which has been prepared as described in Example 2, is introduced, while stirring, into 1.5 mols (134 g) of 'ymethoxypropylamine which has first been heated to 95 C. This reaction mixture is kept at 95 C for 20 minutes, cooled and poured into 1.250 liters of ice water. This is acidified with hydrochloric acid, dried, and washing with water yields 25 vg of 1--ymethoxypropylamino-2-nitro-4-(N-methyl-N- 40 acety1)amino benzene which, after recrystallization,

melts in toluene at C. Analysis of this product yields the following results:

Analysis Calculated for Found CIIIHIDNXIOI C 7c 55.52 55.77 55.54 H 6.76 6.85 6.83 N 7: 14.95 15.11 15.01

EXAMPLE 4 Preparation of 1-N-'y-hydroxypropylamino-2-nitro-4- (N-methyl-N-acetyl)-amino benzene.

0.1 mol (22.9 g) of 2-nitro-4-(N-methyl-N-acetyl) amino chlorobenzene, prepared as described in Example 2 is introduced, while stirring, into 2 mols (150 g) of propanolamine, which has first been heated to C. When this addition has been completed, the mixture is kept at 95 C for 10 minutes, cooled, and poured into 1.5 liters of ice water. It is then acidified with hydrochloric acid, whereupon drying and washing with water yields 25 g of 1-y-hydroxypropylamino-2-nitro-4-(N- methyl-N-acetyl)-amino benzene which, after recrystallization in toluene, melts at 122 C. Analysis of this product yields the following results:

Analysis Calculated for Found l2 l1 I1 4 Several examples will now be given showing how the compounds of formula (1) are used in hair dyeing compositions.

EXAMPLE 5 EXAMPLE 6 The following composition is prepared: l-N -y-hydroxypropylamino-Z-nitro-4-( N-methyl-N- acetyl)-amino benzene- 1.3 g lsooctylphenylpolyethoxyethanol 1.5 g

Water, q.s.p. 100 g This composition is applied to 100 percent white hair for minutes. The hair is then rinsed and shampooed and a deep blonde shade results. 5 What is claimed is:

1. A compound of the formula l l 5 H-N-Rl (I) wherein R is alkyl having 1 6 carbon atoms and R is selected from the group consisting of hydroxyalky] and methoxyalkyl, wherein the alkyl moities have 1 6 carbon atoms.

2. 1-y-methoxypropylamino-2-nitro-4-(N-methyl-N-.

acetyl)amino benzene.

3. l-N-'y-hydroxypropylamino-2-nitro-4-(N-methyl- N-acetyhamino benzene.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,742,048 Dated June 26, 1973 Gregoire KALOPISSIS, Andree BUGAUT and Inventor(s) Vahan ZORAYAN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading Under [75] Inventors, change "Kalopissis Gregoire" to Gregoire KALOPISSIS-- "Bugaut Andree" to Andree BUGAUT "Zorayan Vahan" to Vaha'n zoRAYAN Please insert:-

-- Claims priority, applications Luxembourg, May 16, 1967,

Nos. 53676, 53677 and 53678 Signed and sealed this 17th day of September 1974.

(SEAL) Attest:

MCCOY Mo GIBSON JR. Attesting Officer C. MARSHALL DANN Commissioner of Patents M PO-IOSO (10-69) 

2. 1- gamma -methoxypropylamino-2-nitro-4-(N-methyl-N-acetyl)amino benzene.
 3. 1-N- gamma -hydroxypropylamino-2-nitro-4-(N-methyl-N-acetyl)amino benzene. 